IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Abstract

(+)-Catechin—laccase oxidation dimeric standards were hemi-synthesized using laccase from Trametes versicolor in a water-ethanol solution at pH 3.6. Eight fractions corresponding to eight potential oxidation dimeric products were detected. The fractions profiles were compared with profiles obtained with two other oxidoreductases: polyphenoloxidase extracted from grapes and laccase from Botrytis cinerea. The profiles were very similar, although some minor differences suggested possible dissimilarities in the reactivity of these enzymes. Five fractions were then isolated and analyzed by 1D and 2D NMR spectroscopy. The addition of traces of cadmium nitrate in the samples solubilized in acetone-d6 led to fully resolved NMR signals of phenolic protons, allowing the unambiguous structural determination of six reaction products, one of the fractions containing two enantiomers. These products were then analyzed in grape seed extracts and red wines (UHPLC-Q-Orbitrap MS). The different dimers had different fragmentation patterns according to their interflavan linkage position. Oxidation dimeric compounds had a specific fragment ion at m/z 393, missing for B-Type dimers fragmentations. A fragment ion at m/z 291 occurred and was specific for oxidation dimeric compounds with a C-O-C linkage. Higher level oxidation products had abundant specific fragments: m/z 425, 397 and 245. These fragmentations were useful to identify them in complex samples such as grape seed extracts and wines. Three grape varieties and three ripening stages were selected and the corresponding seed extracts were obtained. The analyses revealed an increasing trend for the oxidation markers during grape ripening. The analysis of Syrah wines (2018, 2014, 2010) showed a decreasing trend of these molecules during wine ageing which might be due to further oxidation.

DOI:

Publication date: June 23, 2022

Issue: IVAS 2022

Type: Article

Authors

Saucier Cedric1, Deshaies Stacy1, Le Guernevé Christine1,2, Sommerer Nicolas1,2, Garcia Lucas Suc François1, Mouls Laetitia1

1SPO, Université de Montpellier, INRAE, Institut Agro, UMR SPO, Faculté de Pharmacie, 15 avenue Charles Flahault, 34000 Montpellier, France
2INRAE, PROBE Research Infrastructure, PFP Polyphenol Facility, 34060 Montpellier, France

Contact the author

Keywords

wine, grape, polyphenol,oxidation, catechin

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Copper contamination in vineyard soils of Bordeaux: spatial risk assessment for the replanting of vines and crops

Copper (Cu) is widely and historically used in viticulture as a fungicide against mildew. Cu has a strong affinity for soil organic matter and accumulates in topsoil horizons. Thus, Cu may negatively affect soil organisms and plants, consequently reducing soil fertility and productivity. The Bordeaux vineyards have the largest vineyard surfaces (26%) within French controlled appellation and a great proportion of French wine production (around 5 million hl per year). Considering the local context of vineyard surfaces decreasing (vine uprooting) and possible new crop plantation, the issue of Cu potential toxicity rises. Therefore, the aims of this work are firstly to evaluate the Cu contamination in vineyard soils of Bordeaux, secondly to produce a risk assessment map for new vine or crop plantation. We used soil analyses from several local studies to build a database with 4496 soil horizon samples. The database was enhanced by means of pedotransfer functions in order to estimate the bioaccessible (EDTA-extractable) Cu in soils of samples without measurements. From this database, 1797 georeferenced samples with CuEDTA concentrations in the topsoil (0-50 cm depth) were used for kriging interpolation in order to produce the spatial distribution map of CuEDTA in vineyard soils. Then, the spatial distribution of Cu was crossed with vine uprooting surfaces and municipality boundaries. CuEDTAconcentrations ranged from 0.52 to 459 mg/kg and showed clear anomalies. Our results from spatial analysis showed that almost 50% of vineyard soil surfaces have CuEDTA concentrations higher than 30 mg/kg (moderate risk for new plantation) and 20% with concentrations higher than 50 mg/kg (high risk for new plantation). A decision-support map based on municipalities was realised to provide a simple tool to stakeholders concerned by land use management.

Mesoclimate impact on Tannat in the Atlantic terroir of Uruguay

The study of climate is relevant as an element conditioning the typicity of a product, its quality and sustainability over the years. The grapevine development and growth and the final grape and wine composition are closely related to temperature, while climate components vary at mesoscale according to topography and/or proximity to large bodies of water. The objective of this work is to assess the mesoclimate of the Atlantic region of Uruguay and to determine the effect of topography and the ocean on temperature and consequently on Tannat grapevine behavior.

Under-vine management effects on grapevine production, soil properties and plant communities in South Australia

Under-vine (UV) management has traditionally consisted of synthetic herbicide use to limit competition between weeds and grapevines. With growing global interest towards non-synthetic chemical use, this study aimed to capture the effects of alternative UV management at two commercial Shiraz vineyards in South Australia, where the sole management variables were UV management since 2016. In adjacent treatment blocks, cultivation (CU) was compared to spontaneous vegetation (SV) in McLaren Vale (MV), and herbicide was compared to SV in Eden Valley (EV). Soil water infiltration rates were slower and grapevine stem water potential was lower in CU compared to SV in MV, with the latter having a plant community dominated by soursob (Oxalis pes-caprae) during winter; while in EV, there was little separation between the treatments. Yields were affected at both sites, with SV being higher in MV and HE being higher in EV. In MV, the only effect on grape must was a lower 13C:12C isotope ratio in CU, indicating greater grapevine water stress. In the grape must at EV, SV had higher total soluble solids, total phenolics, anthocyanins, and yeast available nitrogen; and lower pH and titratable acidity. Pruning weights were not affected by the treatments in MV, while they were higher in HE at EV. Assessments revealed that the differing soil types at the two sites were likely the main determinants of the opposing production outcomes associated with UV management. In the silty loam soil of MV, the higher yields in SV were likely due to more plant-available water, as a potential result of the continuous soil bio-pores formed by winter UV vegetation. Conversely, in the loamy sand soils of EV with a lower cation exchange capacity, the lower yields and pruning weights in SV suggest the UV vegetation competed significantly with the grapevines for available water and nutrients.

Impact of yeast derivatives to increase the phenolic maturity and aroma intensity of wine

Using viticultural and enological techniques to increase aromatics in white wine is a prized yet challenging technique for commercial wine producers. Equally difficult are challenges encountered in hastening phenolic maturity and thereby increasing color intensity in red wines. The ability to alter organoleptic and visual properties of wines plays a decisive role in vintages in which grapes are not able to reach full maturity, which is seen increasingly more often as a result of climate change. A new, yeast-based product on the viticultural market may give the opportunity to increase sensory properties of finished wines. Manufacturer packaging claims these yeast derivatives intensify wine aromas of white grape varieties, as well as improve phenolic ripeness of red varieties, but the effects of this application have been little researched until now. The current study applied the yeast derivative, according to the manufacture’s instructions, to the leaves of both neutral and aromatic white wine varieties, as well as on structured red wine varieties. Chemical parameters and volatile aromatics were analyzed in grape musts and finished wines, and all wines were subjected to sensory analysis by a tasting panel. Collective results of all analyses showed that the application of the yeast derivative in the vineyard showed no effect across all varieties examined, and did not intensify white wine aromatics, nor improve phenolic ripeness and color intensity in red wine.

Deconstructing the soil component of terroir: from controversy to consensus

Wine terroir describes the collectively recognized relation between a geographical area and the distinctive organoleptic characteristics of the wines produced in it. The overriding objective in terroir studies is therefore to provide scientific proof relating the properties of terroir components to wine quality and typicity. In scientific circles, the role of climate (macro-, meso- and micro-) on grape and wine characteristics is well documented and accepted as the most critical. Moreover, there has been increasing interest in recent years about new elements with possible importance in shaping wine terroir like berry/leaf/soil microbiology or even aromatic plants in proximity to the vineyard conferring flavors to the grapes. However, the actual effect of these factors is also dependent on complex interactions with plant material (variety/clone, rootstock, vine age) and with human factors.
The contribution of soil, although a fundamental component of terroir and extremely popular among wine enthusiasts, remains a much-debated issue among researchers. The role of geology is probably the one mostly associated by consumers with the notion of terroir with different parent rocks considered to give birth to different wine styles. However, the relationship between wine properties and the underlying parent material raises a lot of controversy especially regarding the actual existence of rock-derived flavors in the wine (e.g. minerality). As far as the actual soil properties are concerned, the effect of soil physical properties is generally regarded as the most significant (e.g sandy soils being associated with lighter wines while those on clay with colored and tannic ones) mostly through control of water availability which ultimately modifies berry ripening conditions either directly by triggering biosynthetic pathways, or indirectly by altering vigor and yield components. The role of soil chemistry seems to be weakly associated to wine sensory characteristic, although N, K, S and Ca, but also soil pH, are often considered important in the overall soil effect.
Recently, in the light of evidence provided by precision agriculture studies reporting a high variability of vineyard soils, the spatial scale should also be taken into consideration in the evaluation of the soil effects on wines. While it is accepted that soil effects become more significant than climate on a local level, it is not clear whether these micro-variations of vineyard soils are determining in the terroir effect. Moreover, as terroir is not a set of only natural factors, the magnitude of the contribution of human-related factors (irrigation, fertilization, soil management) to the soil effect still remains ambiguous. Lastly, a major shortcoming of the majority of works about soil effects on wine characteristics is the absence of connection with actual vine physiological processes since all soil effects on grape and wine chemistry and sensorial properties are ultimately mediated through vine responses.
This article attempts to breakdown the main soil attributes involved in the terroir effect to suggest an improved understanding about soil’s true contribution to wine sensory characteristics. It is proposed that soil parameters per se are not as significant determining factors in the terroir effect but rather their mutual interactions as well as with other natural and human factors included in the terroir concept. Consequently, similarly to bioclimatic indices, composite soil indices (i.e. soil depth, water holding capacity, fertility, temperature etc), incorporating multiple soil parameters, might provide a more accurate and quantifiable means to assess the relative weight of the soil component in the terroir effect.